CN111683650A

CN111683650A - Cationized vesicle and composition thereof

Info

Publication number: CN111683650A
Application number: CN201780097571.3A
Authority: CN
Inventors: 川口春马; 加藤畅浩; 平田直之
Original assignee: Japan Oil Corp; Kimei Lingsu Cosmetics Co ltd
Current assignee: Japan Oil Corp; Kimei Lingsu Cosmetics Co ltd; NOF Corp
Priority date: 2017-12-08
Filing date: 2017-12-08
Publication date: 2020-09-18
Anticipated expiration: 2037-12-08
Also published as: JPWO2019111415A1; WO2019111415A1; KR102281703B1; JP6735426B2; CN111683650B; EP3721866A1; EP3721866A4; KR20200098560A

Abstract

The present invention provides a vesicle composition which has an adsorptive property to skin and hair, can encapsulate various active ingredients, and is suitable for incorporation into cosmetics. Specifically disclosed are a cationized vesicle formed by cationizing a polymer containing 2-methacryloyloxyethyl phosphorylcholine and a specific cationic monomer, a cationized vesicle containing an active ingredient for a cosmetic, which is retained in the cationized vesicle, and a cosmetic containing the same.

Description

Cationized vesicle and composition thereof

Technical Field

The present invention relates to a cationized vesicle that is cationized using a novel cationized substance, and a method for producing the same. In particular, the present invention relates to the use of cationized vesicles as a cosmetic.

Background

Vesicles refer to bodies of cells surrounded by bilayer membranes formed by self-association of amphiphilic molecules, and in particular, vesicles formed of phospholipid bilayer membranes similar to cell membranes are called liposomes. Various substances can be enclosed in the vesicle (liposome). Liposomes are used to deliver substances enclosed inside into cells, and are being studied and developed as carriers in drug delivery technology (DDS: drug delivery system).

Cosmetics using a technology similar to DDS using liposome are advertised in the name of nano cosmetics, nano capsules, and the like. Japanese patent No. 5623076 (patent document 1) describes a vesicle composition using lysophospholipid and an external preparation for skin containing the vesicle dispersion composition. Japanese patent laid-open publication No. 2012-206948 (patent document 2) describes a liposome composition which is stable also in an acidic region, and a cosmetic and a skin external preparation containing the same. In Japanese Kokai publication 2007-176820 and Japanese Kokai publication 2007-176821 (patent documents 3 and 4), it is described that cosmetics are prepared using a powdered phospholipid composition which is dispersible in an aqueous medium to obtain stable liposomes.

In compositions for topical application such as cosmetics, various measures have been taken to improve the penetration of active ingredients into cells.

Cationization refers to positively charging a substance. Skin is negatively charged and therefore tends to adsorb positive substances.

Japanese patent nos. 4950419 and 5220546 (patent documents 5 and 6) describe liposomes in which components are designed to promote the intracellular permeation of substances into skin or hair cells for the purpose of use in cosmetics.

Jp 2006-35036 (patent document 7) describes particles containing an oily agent, in which the oily agent is contained in a water-soluble solid matrix, the oily agent being separated in the form of oil droplets, and an emulsified substance exhibiting cationic properties is contained in water.

Japanese patent laid-open publication No. 2016-108285 (patent document 8) describes cationized vesicles encapsulating minerals as cosmetic active ingredients. As a substance for cationization, it is said that cationized hyaluronic acid excellent in adsorbability to skin and hair is preferable.

Documents of the prior art

Patent document

Patent document 1: patent No. 5623076 "vesicle composition and external preparation for skin"

Patent document 2: japanese unexamined patent publication No. 2012-206948 discloses a liposome composition, and a cosmetic, a skin external preparation using the same, and a method for producing the same "

Patent document 3: japanese patent laid-open No. 2007-176820 "powdered phospholipid composition"

Patent document 4: japanese patent laid-open No. 2007 & 176821 "powdered phospholipid composition"

Patent document 5: patent No. 4950419 "liposomes containing cationic polymers for promoting intracellular permeation"

Patent document 6: patent No. 5220546' hydrated lamellar phase or liposome containing aliphatic monoamine or cationic polymer for promoting intracellular penetration, and cosmetic or pharmaceutical composition containing the same "

Patent document 7: japanese laid-open patent publication No. 2006-35036 "particles containing oily drugs"

Patent document 8: japanese laid-open patent publication 2016-108285 'cationized vesicle and composition thereof'

Disclosure of Invention

Problems to be solved by the invention

Cationic vesicles are easily adsorbed on the skin, and when used to encapsulate a cosmetic active ingredient, can deliver the ingredient efficiently to the skin, and are therefore excellent compositions as cosmetic materials. The present invention addresses the problem of providing cationized vesicles that have high stability and can encapsulate not only minerals but also other various cosmetic active ingredients.

Means for solving the problems

The present inventors have made extensive studies on the composition of a cationized polymer for cationizing vesicles. By using a novel cationized polymer having a composition different from that of a conventional cationized polymer, the following effects are achieved: the present inventors have completed the present invention by improving the stability of cationized vesicles, diversifying the types of encapsulated substances, and increasing the concentration of encapsulated substances.

That is, the present invention relates to a cationized vesicle for addition to cosmetics, which is cationized by a novel cationized polymer. The invention also relates to a method for cationizing vesicles using the novel cationized polymer. The present invention also relates to a method for producing a cationized vesicle using the novel cationized polymer. The invention also relates to novel cationised polymers.

The cationized polymer contains 2-methacryloyloxyethyl phosphorylcholine and a cationic monomer, and the proportion of the cationic monomer in the cationized polymer is preferably 50% or more.

The cationic monomer is preferably (2-hydroxy-3-methacryloxypropyl) trimethyl ammonium chloride, 2- (methacryloxy) ethyltrimethyl ammonium chloride, or N, N-dimethylaminoethyl acrylate benzyl chloride quaternary salt.

The cationized vesicle may be a unilamellar vesicle or a multilamellar vesicle.

The present invention also relates to a cationized vesicle containing an active ingredient, which is obtained by retaining a cosmetic active ingredient in the cationized vesicle.

The active ingredient is preferably a negatively charged substance, and examples thereof include minerals, amino acids, anionic surfactants, vitamins (e.g., vitamin C and its derivatives), and the like.

The present invention also relates to the above-described cationized vesicle having a Zeta potential of +20mV or more.

The invention also relates to a cationized vesicle which has a Zeta potential of more than +20mV and encapsulates the effective component.

The invention also relates to the above cationized vesicle after freeze drying.

The invention also relates to a freeze-dried cationized vesicle which encapsulates the effective component.

The present invention also relates to a cosmetic product comprising: the above-mentioned cationized vesicle, the above-mentioned cationized vesicle encapsulating an active ingredient, or the above-mentioned freeze-dried cationized vesicle or the above-mentioned cationized vesicle encapsulating an active ingredient.

The cosmetic may also contain natural materials.

The invention also relates to a cosmetic for topical application having skin and hair adsorbing properties, characterized in that it comprises: the above-mentioned cationized vesicle, or the above-mentioned cationized vesicle encapsulating an active ingredient, or the above-mentioned freeze-dried cationized vesicle or the above-mentioned cationized vesicle encapsulating an active ingredient.

The present invention also relates to a cosmetic application method comprising applying a cosmetic product to the skin or hair, the cosmetic product comprising: the above-mentioned cationized vesicle, or the above-mentioned cationized vesicle encapsulating an active ingredient, or the above-mentioned freeze-dried cationized vesicle or the above-mentioned cationized vesicle encapsulating an active ingredient.

The above-mentioned beauty treatment method can be carried out in salon (beauty salon) or at home.

Technical effects

The cationized vesicle of the present invention has excellent skin permeability and low skin irritation, and is therefore suitable for incorporation into a functional cosmetic. In addition, the cationized vesicle of the present invention has improved stability compared to conventionally known substances, and the concentration of an encapsulatable substance (for example, an active ingredient such as a mineral) is increased, and the encapsulatable substance is diversified.

According to the present invention, it is possible to contribute to providing a cosmetic excellent in adsorption, penetration and sustaining force.

Detailed Description

1. Vesicle

The vesicles (vesicles) are formed into a spherical structure closed by a double-layer membrane having a hydrophobic tail facing inward and a hydrophilic head facing outward, due to self-association of amphiphilic molecules in water.

Unilamellar vesicles (SLV), also known as "unilamellar vesicles," are spherical vesicles composed of 1 lipid bilayer membrane.

Vesicles that form a structure in which bilayer membranes are multiply stacked are called multilamellar vesicles (MLVs). MLVs are also called "multilamellar vesicles" and are composed of a plurality of lipid bilayer membranes arranged in concentric circles.

Although there are many amphiphilic molecules that can form vesicles, in particular vesicles formed from phospholipids are referred to as liposomes. Vesicles are a generic term for vesicles composed of phospholipids and surfactants. Liposomes are excellent in biocompatibility as are capsules having the same membrane as skin cells.

The membrane of phospholipids is composed of phospholipids, glycerophospholipids, or cyclic phosphatidic acids from egg yolk or soybean, and is initially negatively charged. In addition, the phospholipid may be either synthetic or commercially available.

Further, cholesterol and phospholipids may be bound to adjust the hardness and permeability of lipid bilayer membranes composed of phospholipids.

The vesicle can be prepared by a conventional production method generally known as a method for producing a liposome.

As a method for producing liposomes, the following methods are known: bangham (j.mol.biol., 13, 238(1965)) et al, or variants thereof, sonication (biochem.biophysis.res.commun., 94, 1367(1980)), ethanol injection (j.cell.biol., 66, 621(1975)), french press method (FEBS lett., 99, 210(1979)), ether injection (n.y.acad.sci., 308, 25O (1978)), cholic acid (surfactant) fusion (biochem.biophysis.acta, 455, 322(1976)), calcium fusion (biochem.biophysis.acta, 394, 483(1978)), freeze-thaw method (arth.biophysis.biophysis, 186(1981)), reverse phase evaporation (proc.n.a.s.usa, 75, 4194(1978)), and use of glass filter (stemp filter method (1975)), and method of using a filter (stemp.biochem)

And a commercially available kit.

2. Cationization

Cationization refers to positively charging a substance. Since the cationized vesicles are positively charged, it is desirable that they adsorb and penetrate into the skin more easily than non-cationized vesicles. In the present invention, it is desirable that the vesicles be cationized to such an extent that such an effect is obtained. Specifically, the Zeta (Zeta) potential of the cationized vesicle is +20my or more, preferably +30mV or more. It is expected that the Zeta potential of the cationized vesicle will also remain stable in the case where an excipient is added for storage, lyophilized, and then re-dissolved in an aqueous solvent. In the present specification, both MLV and SLV are referred to as "cationized vesicles" of the present invention without particular distinction. The cationized MLV may be abbreviated as "CMLV" and the cationized SLV may be abbreviated as "CSLV".

To cationize the vesicles, cationized molecules are used. In general, a cationized polymer is used as the cationized molecule. The cationized vesicle is obtained by adding a cationized molecule (cationized polymer) to the vesicle at the time of preparing the vesicle to cationize the vesicle. The cationized polymer is a polymer substance that is cationized by introducing a cationic group. The cationized polymer itself needs to be biocompatible and, in addition, preferably has a moisturizing effect on the skin and hair.

In the present invention, a cationized polymer comprising a polymer of 2-Methacryloyloxyethyl Phosphorylcholine (MPC) and a specific cationic monomer is used. MPC has both a structure identical to a cell membrane and a polymerizable structure, has extremely high affinity for an organism, and is an epoch-making biocompatible material.

Examples of cationic monomers include:

ブレンマ

QA: (2-hydroxy-3-methacryloxypropyl) trimethylammonium chloride;

MOETAC: 2- (methacryloyloxy) ethyltrimethylammonium chloride;

-BQ: n, N-dimethylaminoethyl acrylate benzyl chloride quaternary salt and the like

One embodiment of the cationized polymer used in the present invention to cationize vesicles is MPC- ブレンマ -QA copolymer. It is prepared from MPC and ブレンマ

The synthetic polymer formed by QA has a component name (name) of "Polyquaternium-64 (Polyquaternium-64)". A typical commercially available polyquaternium-64 is composed of 30% MPC and 70% cationic monomer.

In the present invention, the cationized polymer having a new composition produced in the examples is also preferably used. One embodiment of such a cationized polymer is formed from MPC and ブレンマ

QA formed cationized polymers. Another embodiment is a cationized polymer formed from MPC and MOETAC. Yet another embodiment is a method for generating a MPC and a MPC

-BQ forming cationised polymers. The ratio of MPC to cationic monomer in the cationized polymer, and the molecular weight of the cationized polymer, can be varied widely. In the present invention, the proportion of the cationic monomer in the cationized polymer is preferably 50% or more, and more preferably 55% or more. The present inventors confirmed that even if the proportion of the cationic monomer is increased to 82%, cationized vesicles can be produced. The molecular weight of the cationized polymer is preferably 60 ten thousand or more. The present inventors confirmed that even with a molecular weight of 200 ten thousand, cationized vesicles can be produced.

3. Use of cationized vesicles in cosmetics

When the cationized vesicle encapsulating the cosmetic active ingredient is added to cosmetics such as lotion, beauty lotion, emulsion, cream, shampoo, etc., the ingredient can be effectively delivered to the skin.

SLV is suitable for lotions, beauty lotions and the like because it is transparent, and for lotions, creams and the like because MLV is milky white.

The substance encapsulated by the cationized vesicle can be appropriately selected depending on the use of the cosmetic.

Negatively charged substances are generally difficult to encapsulate in vesicles and cationized vesicles. In the cationized vesicle of the present invention, a negatively charged substance may be encapsulated as a cosmetic ingredient. Examples of such encapsulated cosmetic ingredients include ingredients with negative ions such as minerals, amino acids, anionic surfactants, vitamin C and derivatives thereof. In the present specification, a cationized vesicle that retains a cosmetic active ingredient is referred to as a "cationized vesicle that encapsulates an active ingredient".

Examples of the minerals include: the deep sea water concentrated composition described in Japanese patent laid-open No. 2007 and 217356, the deep sea water described in Japanese patent laid-open No. 2000 and 290159, or the extract of Broussonetia (Yunohana) described in Japanese patent laid-open No. 3967357. In the present specification, a cationized vesicle in which a deep sea water concentrate composition, a dried product of deep sea water or a dried product thereof, or a flower extract of soup is enclosed is referred to as a "mineral-encapsulated cationized vesicle".

For example, the deep-sea water concentrate is an NF membrane permeated water concentrate obtained by a manufacturing method comprising the following steps (1) and (2):

(1) treating the deep sea water with a nanofiltration membrane capable of removing more than 90% of sulfate ions to obtain a product having Brix (Brix) of 2.8 to 3.6, Mg ion concentration of 300 to 900Mg/L, Ca ion concentration of 200 to 600Mg/L, and SO₄A step of allowing the NF membrane with the ion concentration of 0-300 mg/L to permeate water; and

(2) concentrating the NF membrane permeated water obtained in the step (1) to obtain a product having a Brix of 30.0 to 55.0, a Mg ion concentration of 10,000 to 100,000Mg/L, Ca, an ion concentration of 4,000 to 40,000Mg/L, and SO₄Concentrating the permeated water with NF membrane having ion concentration of 0-1,000 Mg/L and Ca ion concentration and Mg ion concentration of 1: 0.25-1: 4And (5) a step of preparing the product.

The concentration of the NF membrane permeated water is preferably an aqueous solution which is 14 to 50 times concentrated and in which the NF membrane permeated water concentrate is not precipitated. Further, for example, the nanofiltration membrane preferably has a pore diameter of 0.1 to 1nm and a pressure applied to the membrane of 0.3 to 2. OMPa.

For example, the extract of soup flower (Yunohana) is a composition containing an ozone-oxidized product of soup flower obtained by a production method including the following steps (1) to (3):

(1) crystallizing hot spring air jet on the clay under constant temperature and constant humidity to obtain soup flower (hot spring flower),

(2) dissolving the flower of soup in an aqueous solvent, and then

(3) And carrying out ozone oxidation treatment on the dissolved substance to obtain an ozone oxidation treatment substance.

The flower extract of the soup preferably contains (1) 25 to 40,000mg/L of sulfate ion; (2) 5.0-8,000 mg/L of 3-valent iron ions; and (3) aluminum ions; and the valence 2 iron ion: the ratio of the 3-valent iron ions is 4,900: 2,000 or less. Here, the amount of the 2-valent iron ion is 0.5 or less relative to the amount of the 3-valent iron ion 1.

In the present specification, the deep sea water concentrate composition, the deep sea water, the dried seawater, and the flower extract of soup are also referred to simply as "minerals".

The concentration of minerals that the cationized vesicles of the present invention can encapsulate is increased over the past. The concentration of the encapsulatable mineral is about 0.0001% to about 5%, for example, about 0.1% to about 5%, about 2% to about 5%, about 3% to about 5%, by weight%, relative to the total weight of the vesicle.

In addition, the cationized vesicles of the present invention can encapsulate a wide variety of substances. As examples of the encapsulated cosmetic ingredient, in addition to the above minerals, vitamin C derivatives (e.g., sodium ascorbyl phosphate) and the like can be cited. The vitamin C derivative can be encapsulated at a concentration of about 0.1% to about 5% by weight relative to the total weight of the vesicle. The cationized vesicle encapsulating the active ingredient can be produced by the following method: the encapsulated active ingredient (e.g., minerals, amino acids, anionic surfactants, vitamin C and derivatives thereof), the cationized polymer, the phospholipid, the surfactant, and, if desired, other cosmetic ingredients are stirred and mixed with an aqueous solvent (purified water or seawater) at a temperature of about 80 ℃ (e.g., 75 to 85 ℃), and then gradually cooled to about room temperature to about 35 ℃. In addition, the liposome can be suitably produced by using a technique known as a method for producing the liposome. The cooled composition may also be emulsified at elevated pressure (e.g., 220MPa × 5Pass) and filtered (e.g., with a 1.0 μm filter).

Among the other cosmetic ingredients mentioned above, there may be mentioned: moisturizing components, extracts of crude drugs, enzymes such as tyrosinase, superoxide dismutase and lipase, vitamins such as retinol, ascorbic acid, tocopherol, pyridoxal and riboflavin or derivatives thereof, organic pigments such as β -carotene and chlorophyll, moisturizing components such as glycerin, sorbitol, urea, lactic acid, propylene glycol, polyethylene glycol and copolymers, and glucose derivatives, skin caring components such as paraffin, stearyl alcohol, cetyl alcohol, squalane, silicone oil and stearate, caring components, anti-dandruff components, hair caring and hair growing components, ultraviolet absorbents, antioxidants, perfumes, preservatives, and the like. These may be used in combination of 2 or more kinds as required.

The cosmetic of the present invention can be produced by adding 1 or more cationic vesicles encapsulating active ingredients to a formulation of a usual lotion, a beauty lotion, an emulsion, a cream, a shampoo, or the like. The form of the cosmetic is not particularly limited, but it is preferably applied to the skin or hair. Topical application also includes rinsing the skin or hair after application. For example, the following can be prepared: examples of the cosmetic composition include face toilet, cleanser, skin lotion, beauty lotion, pack, massage cream, milky lotion, moisturizer, lipstick, etc., as a skin care cosmetic, foundation, white powder, lipstick, blush, eye shadow, etc., as a color cosmetic, soap, liquid cleanser, bathing agent, etc., as a body care cosmetic, shampoo, hair conditioner, hair care agent, hair setting agent, hair tonic, hair restoration agent, scalp care agent, etc., as a hair care cosmetic. The cosmetic may contain various cosmetic ingredients (oils, waxes, hydrocarbons, fatty acids, alcohols, esters, amino acids, vitamins, surfactants, pH adjusters, preservatives, perfumes, moisturizers, powders, ultraviolet absorbers, thickeners, pigments, antioxidants, whitening agents, anti-inflammatory agents, anti-wrinkle agents, skin roughness improvers, acne remedies, alkalis, chelating agents, metal-blocking agents (metal chelating agents), and the like) which are generally used in cosmetics, as long as the desired effects are not impaired.

As shown in examples described later, the cosmetic of the present invention may further contain a natural product. Examples of such substances are as follows. The plum extract described in patent No. 4795475 is, for example, a plum root extract or plum fruit distilled water. Japanese patent No. 2526362 discloses a plum juice fermentation broth. The steam distilled water derived from a plant described in Japanese patent laid-open No. 2012-116761 is, for example, 1 or 2 or more kinds of steam distilled water selected from passion fruit (Passiflora edulis Sims), kumquat (Citrus depressa Hayata), banana, hybrid custard apple (Annona atemoya), plum, mandarin orange (Citrus Tankan Hayata), lemon-lime, and ginger. An angelica sinensis extract described in japanese patent No. 3544505. A yeast culture derived from seawater as described in Japanese patent laid-open No. 2009-029788.

Examples

The present invention will be specifically described below with reference to examples. The examples are given solely for the purpose of illustration and are not intended to limit the scope of the invention.

Example 1: preparation of cationized Polymer

16.6g of MPC and 33.4g of ブレンマ

QA was dissolved in 200g of water, the resulting solution was put into a four-necked flask, nitrogen gas was blown thereinto for 30 minutes, and then a polymerization initiator (VA-061 manufactured by Wako pure chemical industries, Ltd., 0.55g) was added thereto at 75 ℃ to conduct polymerization for 10 hours. Dropping 5 the polymerization solution while stirringThe precipitated precipitate was filtered off in L ether, and vacuum-dried at room temperature for 48 hours to obtain 30.1g of a cationized polymer powder. Thus, a molecular weight of 70 ten thousand, from 45% MPC and 55% ブレンマ was obtained

A cationized polymer (polyquaternium-64) composed of QA (MPC/cation: 45/55). In addition, by the same method, cationic polymers having different molecular weights and ratios of MPC to ブレンマ -QA, and cationic polymers having different cationic monomers containing MPC and MOETAC or DMAEQ-BQ were obtained.

Example 2: preparation and evaluation of stability of mineral-encapsulated cationized vesicles

Mineral-encapsulated cationized vesicles were prepared from the following.

Hydrogenated cyclic lyso-sodium phosphatide/hydrogenated lecithin/cholesterol: 1 percent;

an encapsulate (labeled "mineral" in table 1) and a chelator that dissolves the encapsulate;

various cationized polymers made in example 1: 3 percent;

PCA cocoyl arginine ethyl ester as preservative: 0.02 percent

As an example of the raw material of the charged negative ion, a mineral (flower extract of soup) is used as the encapsulate. Stability was evaluated for mineral-encapsulated cationized vesicles containing various cationized polymers, in which 0.01% to 1% of a mineral (flower extract of soup) was encapsulated with a chelating agent. The Zeta potential fluctuation in the presence or absence of the cationized substance derived from the polyquaternium-64 was measured. Aggregation/precipitation was determined visually. The results are shown in Table 1. The particle size is judged to be large when the Z-average value or the 1 st peak of the scattering intensity is 200nm or more.

The Zeta potential of a typical vesicle (EXTRASOME CP-7M, tables 13 and 127) is negative. In known cationized vesicles (Lipidure C, 17 in the table), stability is significantly impaired when 0.01% of mineral is encapsulated, resulting in precipitation and aggregation. A mineral-encapsulated cationized vesicle having a Zeta potential of +20mV or more and being stable for several days or more is obtained by using a cationized polymer having a cation ratio of 50% or more and a molecular weight of 60 ten thousand or more.

Example 3: preservation of mineral-encapsulated cationized vesicles by lyophilization

The mineral-encapsulated cationized vesicle prepared in example 2 was mixed with 10%

(highly branched cyclodextrin) and refined water at a ratio of 1: 3: 6, and stirring. Then, the mixture was frozen at-20 ℃ or lower, and freeze-dried.

As for the particle size, the ratio of the original solution of the mineral-encapsulated cationized vesicle to that of the original solution of the mineral-encapsulated cationized vesicle was 10% by weight of that of the original solution for lyophilization

The Zeta potential was stable in both the pre-frozen state of the mix and the state of redissolution in purified water after freeze-drying (data not shown).

Example 4: usefulness test

Instead of the envelope, a skin permeability test was performed using a fluorescent dye. EpiSkin dispensed from a 12-well plate containing 2mL of PBS was dispensed at 300. mu.L of 0.01% calcein and SLV, MLV, CSLV, CMLV encapsulating 0.01% calcein^TMThe stratum corneum side of the Large Model (EpiSkin) was activated and the incubation was continued at 37 ℃ for 6 hours and 24 hours. After the action, the skin was washed with purified water, transferred to a test tube together with stainless steel beads and 1mL of purified water, and pulverized with TissueLyser. The supernatant was obtained by centrifugation, the fluorescence intensity was measured (Ex/Em ═ 494/520nm), the amount of calcein in the skin was calculated, and the skin permeation effect was evaluated. In addition, the fluorescence intensity of PBS in a 12-well plate (Ex/Em: 494/520nm) was measured in the same manner, and the transdermal effect was evaluated.

The results are shown in Table 2. Both CSLV and CMLV have higher skin permeation effect and skin permeation effect than SLV and MLV.

[ Table 2]

Example 5: observation with an electron microscope

SLV, MLV, CSLV and CMLV were observed by a transmission electron microscope. SLV and CSLV were confirmed to be single-layer, while MLV and CMLV had a multilayer structure.

Example 6: spot test)

A24-hour closed patch test was carried out by 20 Japanese using patch tape coated with a cationized polymer, CSLV, CMLV. As a negative object, vaseline, physiological saline, and purified water were used, and after peeling off the patch tape for 1 hour, the erythema state was determined from the negative object and the following criteria, and the skin irritation index was calculated using the following formula. The test articles were classified according to the following table based on the skin irritation index.

Skin irritation index (sum of scores/number of subjects x 100)

[ Table 3]

Criterion for determination	Scoring	Reaction of
			-	0	No reaction
±	0.5	Mild erythema
			+	1.0	Erythema
++	2.0	Erythema, edema, papules
			+++	3.0	Erythema, edema, papule, small blisters
++++	4.0	Blister (blister)

The results are shown in Table 4 below.

[ Table 4]

Index of skin irritation	Classification
		5.0 or less	Security article
5.0～15.0	Permissive article
		15.0～30.0	To be improved
30.0 or more	Hazardous article

All 3 kinds of inspection products are classified as "safety products".

[ production example of cationized vesicle (pretreatment) encapsulating active ingredient ]

Mineral-encapsulated cationized vesicles 1

[ Table 5]

Manufacturing method

Heating the water phase A to 75 ℃, and emulsifying by using an emulsifying machine.

After cooling to 35 ℃, high pressure treatment (220MPa × 5pass) was performed to obtain the mineral-encapsulated cationized vesicle 1.

Mineral-encapsulated cationized vesicles 2

[ Table 6]

Manufacturing method

After cooling to 35 ℃, high pressure treatment (220MPa × 5pass) was performed to obtain the mineral-encapsulated cationized vesicles 2.

Cationized vesicle encapsulating vitamin C derivative

[ Table 7]

Manufacturing method

After cooling to 35 ℃, high pressure treatment (220MPa × 5pass) was performed to obtain the vitamin-encapsulated cationized vesicles.

[ production example of cosmetic preparation ]

Cream

[ Table 8]

Manufacturing method

Heating the aqueous phase A to 75 ℃, and stirring to dissolve.

Heating the oil phase B to 85 ℃, and stirring to dissolve.

Adding cream and oil phase B into water phase A, heating to 80 deg.C, and emulsifying with emulsifying machine.

Cooled to 45 ℃ and aqueous phase C was added thereto for neutralization.

Cooling to 35 deg.C to obtain cream.

Lotion formulation

[ Table 9]

Manufacturing method

Heating the aqueous phase A to 75 ℃, and stirring to dissolve.

The aqueous phase A was cooled to 40 ℃ and the pretreated B was added thereto with stirring.

Then, aqueous phase C was added thereto to neutralize.

Cooling to 35 deg.C to obtain lotion.

Beauty liquid

[ Table 10]

Manufacturing method

Heating the aqueous phase A to 80 ℃, and stirring to dissolve.

After cooling to 40 ℃, aqueous phase B was added thereto.

And adding a cosmetic liquid to the mixture to pretreat the mixture C.

Cooling to 35 deg.C to obtain skin caring liquid.

Mineral cream

[ Table 11]

Manufacturing method

Heating the aqueous phase A to 80 ℃, and stirring to dissolve.

Pretreated B, C was added thereto, heated to 80 ℃ and dissolved with stirring.

Heating the oil phase E to 90 ℃, and stirring to dissolve.

Adding oil phase E into water phase A, heating to 80 deg.C, and emulsifying with emulsifying machine.

Cooled to 45 ℃ and aqueous phase F was added thereto for neutralization.

Cooling to 35 deg.C to obtain cream.

Mineral lotion

[ Table 12]

Manufacturing method

Heating the aqueous phase A to 80 ℃, and stirring to dissolve.

Cooled to 40 ℃, pretreated B, C was added thereto and stirred.

Then, aqueous phase D was added thereto for neutralization.

Cooling to 35 deg.C to obtain mineral lotion.

Hair washing agent

[ Table 13]

Manufacturing method

Heating the aqueous phase A to 80 ℃, and stirring to dissolve.

Aqueous phase B was heated to 75 ℃ and added with stirring to dissolve.

The aqueous phase C was heated to 60 ℃ and added dissolved with stirring.

After cooling to 40 ℃, aqueous phase D was added thereto.

Cooling to 35 deg.C to obtain shampoo.

Body lotion (body nursing lotion)

[ Table 14]

Manufacturing method

Heating the water phase A to 70 ℃, and stirring to dissolve.

Heating oil phase B to 80 deg.C, stirring to dissolve.

Adding the emulsion pretreatment B and the oil phase B into the water phase A, heating to 75 ℃, and emulsifying by using an emulsifying machine.

To this was added aqueous phase C for neutralization.

Cooled to 40 ℃ and aqueous phase D was added thereto.

Cooling to 35 deg.C to obtain body milk.

Claims

1. A cationized vesicle for addition to cosmetics, which is cationized with a cationized polymer containing 2-methacryloyloxyethyl phosphorylcholine and a cationic monomer, wherein the cationic monomer is contained in the cationized polymer in a proportion of 50% or more.

2. The cationized vesicle of claim 1, which is a unilamellar vesicle or a multilamellar vesicle.

3. The cationized vesicle of claim 1 or 2, wherein the cationic monomer is:

(2-hydroxy-3-methacryloxypropyl) trimethyl ammonium chloride,

2- (methacryloyloxy) ethyltrimethylammonium chloride, or

Benzyl chloride quaternary salt of N, N-dimethylaminoethyl acrylate.

4. A cationized vesicle encapsulating an active ingredient, wherein a cosmetic active ingredient is retained in the cationized vesicle according to any one of claims 1 to 3.

5. The cationized vesicle encapsulating an active ingredient according to claim 4, wherein the active ingredient is a mineral.

6. The cationized vesicle encapsulating an active ingredient according to claim 4, wherein the active ingredient is vitamin C or a vitamin C derivative.

7. The cationized vesicle according to any one of claims 1 to 3 or the cationized vesicle encapsulating an active ingredient according to any one of claims 4 to 6, wherein the Zeta potential is +20mV or more.

8. The cationized vesicle according to any one of claims 1 to 3 or the cationized vesicle encapsulating an active ingredient according to any one of claims 4 to 6, which is freeze-dried.

9. A cosmetic comprising a cationized vesicle, wherein the cationized vesicle is the cationized vesicle according to any one of claims 1 to 3, or the cationized vesicle encapsulating an active ingredient according to any one of claims 4 to 6, or the freeze-dried cationized vesicle according to claim 8 or the cationized vesicle encapsulating an active ingredient.

10. The cosmetic of claim 9, which is adsorptive to skin and hair, topically applied.

11. A method of cosmetic application comprising applying the cosmetic of claim 9 to skin or hair.